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EP1444297B1 - Flammwidrige thermoplastharzzusammensetzung - Google Patents

Flammwidrige thermoplastharzzusammensetzung Download PDF

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Publication number
EP1444297B1
EP1444297B1 EP01982910A EP01982910A EP1444297B1 EP 1444297 B1 EP1444297 B1 EP 1444297B1 EP 01982910 A EP01982910 A EP 01982910A EP 01982910 A EP01982910 A EP 01982910A EP 1444297 B1 EP1444297 B1 EP 1444297B1
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EP
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Prior art keywords
weight
parts
alkyl
flame retardant
group
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EP01982910A
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English (en)
French (fr)
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EP1444297A4 (de
EP1444297A1 (de
Inventor
Jong Cheol Chem. Division R. & D. Center Lim
Sang Hyun Chem. Division R. & D. Center Hong
Kyung Hoon Chem. Division R. & D. Center Seo
Sam Joo Chemicals Division R. & D. Center Yang
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Cheil Industries Inc
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Cheil Industries Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

  • the present invention relates to a polycarbonate thermoplastic resin composition with good flame retardancy, heat resistance and mechanical properties. More particularly, the present invention relates to a flame retardant polycarbonate thermoplastic resin composition that comprises a polycarbonate resin, a rubber modified vinyl-grafted copolymer, a phosphorous compound mixture of a cyclic phosphazene oligomer compound and a phosphoric acid ester, as a flame retardant, and a fluorinated polyolefin resin.
  • a blend of a polycarbonate resin and a styrene-containing copolymer is a resin composition which has improved processability maintaining the good notched impact strength.
  • the polycarbonate resin composition should further have good flame retardancy as well as high mechanical strength because the resin composition are applied to electric or electronic goods, automobile parts, office supplies, etc.
  • a halogen-containing flame retardant and/or an antimony-containing compound were used.
  • the disadvantages could be observed that the halogen-containing compound results in the corrosion of the mold itself by the hydrogen halide gases released during the molding process and is fatally harmful due to the toxic gases liberated in case of fire.
  • the polybromodiphenyl ether mainly used for a halogen-containing flame retardant, can produce toxic gases such as dioxin or furan during combustion, flame retardants which are prepared without a halogen-containing compound have become a major concern in this field.
  • a general method is employ a phosphoric acid ester compound as a flame retardant to provide the polycarbonate resin with flame retardancy without using a halogen-containing compound.
  • U.S. Patent No. 4,692,488 discloses a thermoplastic resin composition comprising a halogen free aromatic polycarbonate resin, a halogen free SAN (styrene-acrylonitrile) copolymer, halogen free phosphorus compounds as flame retardants, a tetrafluoroethylene polymer and a small amount of ABS (acrylonitrile-butadiene-styrene) copolymer. If a halogen free phosphorus compound and a tetrafluoroethylene polymer are used together as in this U.S. patent, the dripping phenomenon can be prevented, but a juicing phenomenon occurs due to the migration of the flame retardant agent to the surface of the molded article during molding process.
  • U.S. Patent No. 5,061,745 discloses a thermoplastic resin composition comprising an aromatic polycarbonate resin, an ABS graft copolymer, a copolymer, and a monophosphorous ester.
  • the flame retardant agent is monomeric, the juicing phenomenon is not prevented and the heat resistance is rapidly deteriorated.
  • Japanese Patent Publication No. 59-202,240 discloses a method of preparing an oligomeric phosphate and the use of the oligomeric phosphate in a polyamide or polycarbonate resin composition.
  • U.S. Patent No. 5,204,394 discloses a resin composition comprising an aromatic polycarbonate resin, a styrene-containing copolymer or a graft copolymer, and oligomeric phosphate as flame retardants.
  • the resin composition improves the juicing phenomenon and heat resistance, but is inferior to the resin composition using the monophosphorous esters as flame retardants in flame retardancy. Accordingly, to maintain a good flame retardancy, the resin composition should contain more flame retardants than in the resin composition containing monophosphorous ester as flame retardants. As a result, the resin composition shows poor mechanical properties due to the high content of a flame retardant. Furthermore, the resin composition contains still some monophosphorous ester which migrates to the surface of the molded article to cause juicing phenomenon in part.
  • U.S. Patent No. 5,672,645 discloses a PC/ABS resin composition
  • a PC/ABS resin composition comprising an aromatic polycarbonate resin, a vinyl copolymer, a graft copolymer, a mixture of a monophosphate and an oligomeric phosphate, and a fluorinated polyolefin.
  • the resin composition shows juicing phenomenon in which monophosphorous ester migrates to the surface of the molded article, and deterioration of heat resistance.
  • the flame retardability of an oligomeric phosphate ester is less than that of a momophosphorous ester in usual, the more oligomeric phosphate ester is contained in the flame retardant agent, the poorer flame retardancy of resin composition is.
  • Japanese Patent Laid-open No. 6-100,785 discloses a flame retardant resin composition which comprises a thermoplastic resin, a phosphate compound, and a silicon resin or a polyphosphazene to prevent from dripping of the resin during combustion.
  • a flame retardant resin composition which comprises a thermoplastic resin, a phosphate compound, and a silicon resin or a polyphosphazene to prevent from dripping of the resin during combustion.
  • the Japanese patent application does not disclose that the flame retardancy of the resin composition had been improved.
  • EP 0 728 811 A2 discloses a thermoplastic resin composition comprising an aromatic polycarbonate, a graft copolymer, a copolymer and a phosphazene.
  • the European patent teaches that no dripping occurs during combustion by using a phosphazene as a flame retardant even though an additional anti-dripping agent is not employed, and that the resin composition has excellent heat resistance and impact strength.
  • the resin composition of the European patent has a poor processability due to the poor flowability by using the phosphazene, and causes black stripes and/or black lines on the surface of the molded article due to degradation of the resin or flame retardants when an excess stress is applied to the article during molding.
  • mechanical strength such as flexural strength and flexural modulus becomes deteriorated, and more amount of flame retardants should be used to maintain a certain degree of flame retardancy.
  • WO 00/09518 and WO 99/19383 disclose methods of preparing a cross-linked linear or cyclic phenoxy phosphazene and a thermoplastic resin composition using such phosphazene compounds.
  • the cross-linked phenoxy phosphazene does not deteriorate the mechanical properties of the resin composition when applied, because the phosphazene has a high melting point and lower volatility.
  • the resin composition of the patent applications has a poor processability due to the poor flowability by using the phosphazene, and causes black stripes and/or black lines on the surface of the molded article due to degradation of the resin or flame retardants when an excess stress is applied to the article during molding.
  • mechanical strength such as flexural strength and flexural modulus becomes deteriorated.
  • the present inventors have developed a flame retardant thermoplastic resin composition that comprises a polycarbonate resin, a rubber modified vinyl-grafted copolymer, a vinyl copolymer, an oligomer type cyclic phosphazene compound and a phosphoric acid ester as a flame retardant and a fluorinated polyolefin resin, which has a good balance of physical properties such as impact strength, heat resistance, heat stability, processability and appearance.
  • a feature of the present invention is the provision of an excellent flame retardant thermoplastic resin composition.
  • Another feature of the present invention is the provision of a flame retardant thermoplastic resin composition with good heat resistance.
  • a further feature of the present invention is the provision of a flame retardant thermoplastic resin composition with good mechanical properties.
  • a further feature of the present invention is the provision of a flame retardant thermoplastic resin composition with a good balance of physical properties such as impact strength, heat stability, processability and appearance.
  • a flame retardant thermoplastic resin composition according to the present invention comprises (A) about 45 to 95 parts by weight of a polycarbonate resin, (B) about 1 to 50 parts by weight of a rubber modified vinyl-grafted copolymer prepared by graft-polymerizing (b 1 ) about 5 to 95 parts by weight of a monomer mixture consisting of about 50 to 95 % by weight of styrene, ⁇ -methylstyrene, halogen- or alkyl-substituted styrene, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, or a mixture thereof and about 5 to 50 % by weight of acrylonitrile, methacrylonitrile, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, maleic acid anhydride, C 1-4 alkyl- or phenyl N-substituted maleimide or a mixture thereof onto (b 2 ) about 5 to
  • a flame retardant thermoplastic resin composition according to the present invention comprises (A) about 45 to 95 parts by weight of a polycarbonate resin, (B) about 1 to 50 parts by weight of a rubber modified vinyl-grafted copolymer, (C) about 0 to 50 parts by weight of a vinyl copolymer, (D) about 1 to 30 parts by weight of a phosphorous mixture of a cyclic phosphazene oligomer compound and a phosphoric acid ester, as a flame retardant, per 100 parts by weight of (A)+(B)+(C), and (E) about 0.05 to 5.0 parts by weight of a fluorinated polyolefin resin per 100 parts by weight of (A)+(B)+(C).
  • the polycarbonate resin is prepared by reacting a diphenol represented by the following formula (I) with a phosgene, a halogen formate or a carboxylic acid diester: where A is a single bond, a C 1-5 alkylene group, a C 1-5 alkylidene group, a C 5-6 cycloalkylidene group, S or SO 2 .
  • diphenol examples include hydroquinone, resorcinol, 4,4'-dihydroxydiphenol, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane.
  • More preferable diphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, and 1,1-bis-(4-hydroxyphenyl)-cyclohexane, and the most preferable diphenol is 2,2-bis-(4-hydroxyphenyl)-propane called 'bisphenol A'.
  • the polycarbonate resin (A) has a weight average molecular weight (M w ) of about 10,000 to 200,000, more preferably about 15,000 to 80,000.
  • a polycarbonate with branched chains may also be preferably used.
  • a compound with 3 valences or above may be added in an amount of about 0.05 to 2 mol % per the total moles of the diphenol to be used.
  • a homopolymer of polycarbonate, a copolymer of polycarbonate or a mixture thereof may be used in this invention.
  • Some portion of the polycarbonate resin may be replaced with an aromatic polyester-carbonate resin that is obtained by polymerization in the presence of an ester precursor, such as difunctional carboxylic acid.
  • the polycarbonate resin is used in an amount of about 45 to 95 parts by weight as per 100 parts by weight of the flame retardant thermoplastic resin composition according to the present invention.
  • the rubber modified vinyl-grafted copolymer according to the resent invention is prepared by graft-polymerizing (b 1 ) about 5 to 95 parts by weight of a monomer mixture consisting of about 50 to 95 % by weight of styrene, ⁇ -methylstyrene, halogen- or alkyl-substituted styrene, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, or a mixture thereof and about 5 to 50 % by weight of acrylonitrile, methacrylonitrile, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, maleic acid anhydride, C 1-4 alkyl- or phenyl N-substituted maleimide or a mixture thereof onto (b 2 ) about 5 to 95 parts by weight of a rubber polymer selected from the group consisting of butadiene rubber, acryl rubber, ethylene-propylene rubber,
  • the C 1-8 methacrylic acid alkyl ester is obtained from methacrylic acid and monohydric alcohol with 1 to 8 carbon atoms and the C 1-8 acrylic acid alkyl ester from acrylic acid and monohydric alcohol with 1 to 8 carbon atoms.
  • the examples of the acid alkyl ester include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, and methacrylic acid propyl ester. Methacrylic acid methyl ester is the most preferable.
  • the rubber modified vinyl-grafted copolymer are gafted-polymers obtained by graft polymerizing a mixture of styrene and acrylonitrile, and, optionally, (meth)acrylic acid alkyl ester onto butadiene rubber, acryl rubber or styrene-butadiene rubber, or by graft polymerizing (meth)acrylic acid alkyl ester onto butadiene rubber, acryl rubber or styrene-butadiene rubber.
  • the most preferable examples of the rubber modified vinyl-grafted copolymer are a grafted-polymer that a mixture of styrene and acrylonitrile is grafted onto butadiene rubber, which is called acrylonitrile-butadiene-styrene (ABS) resin, and a grafted-polymer of MBS resin.
  • ABS acrylonitrile-butadiene-styrene
  • the rubber polymer to prepare the rubber modified vinyl-grafted copolymer has preferably an average particle size of about 0.05 to 4.0 ⁇ m considering the impact strength and appearance.
  • the rubber modified graft copolymer according to the present invention can be prepared through a conventional polymerization process such as emulsion, suspension, solution or bulk process.
  • the copolymer can be preferably prepared through the emulsion or bulk process in which vinyl monomers are added to the rubber polymer using an initiator.
  • the rubber modified vinyl-grafted copolymer is used in an amount of about 1 to 50 parts by weight as per 100 parts by weight of the flame retardant thermoplastic resin composition according to the present invention.
  • the vinyl copolymer of the present invention is a copolymer that is polymerized with (c 1 ) about 50 to 95 % by weight of styrene, ⁇ -methylstyrene, halogen- or alkyl-substituted styrene, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, or a mixture thereof and (c 2 ) about 5 to 50 % by weight of acrylonitrile, methacrylonitrile, C 1-8 methacrylic acid alkyl ester, C 1-8 acrylic acid alkyl ester, maleic acid anhydride, C 1-4 alkyl- or phenyl N-substituted maleimide or a mixture thereof.
  • a mixture of the copolymers may be used as the component (C).
  • the C 1-8 methacrylic acid alkyl ester is obtained from methacrylic acid and monohydric alcohol with 1 to 8 carbon atoms and the C 1-8 acrylic acid alkyl ester from acrylic acid and monohydric alcohol with 1 to 8 carbon atoms.
  • the examples of the acid alkyl ester include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, and methacrylic acid propyl ester. Methacrylic acid methyl ester is the most preferable.
  • the vinyl copolymer can be produced as by-products when preparing the rubber modified vinyl-graned copolymer (B).
  • the by-products are mostly produced when an excess of monomers are grafted onto a small amount of rubber polymer or when a chain transfer agent is used in excess.
  • the amount of the vinyl copolymer to be used in this invention does not include the amount of the by-products that might be produced during preparation of the rubber modified vinyl-grafted copolymer (B).
  • the preferable examples of the vinyl copolymer are a copolymer of styrene and acrylonitrile, a copolymer of ⁇ -methylstyrene and acrylonitrile, and a copolymer of styrene, ⁇ -methylstyrene and acrylonitrile.
  • the vinyl copolymer is preferably prepared by emulsion, suspension, solution or bulk process, and has a weight average molecular weight (M w ) of about 15,000 to 200,000.
  • the vinyl copolymer (C) is a copolymer prepared from a mixture of methacrylic acid methyl ester monomers and optionally acrylic acid methyl ester monomers.
  • the vinyl copolymer is preferably prepared by emulsion, suspension, solution or bulk process, and has a weight average molecular weight (M w ) of about 20,000 to 250,000.
  • a further preferable example of the vinyl copolymer is a copolymer of styrene and maleic acid anhydride, which is prepared by a continuous bulk process or a solution process.
  • the maleic acid anhydride is preferably used in the amount of about 5 to 50 % by weight.
  • the copolymer of styrene and maleic acid anhydride has a weight average molecular weight (M w ) of about 20,000 to 200,000 and an intrinsic viscosity of about 0.3 to 0.9.
  • the styrene for preparation of the component (C) in this invention can be replaced with p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene or ⁇ -methylstyrene.
  • the vinyl copolymer is used in an amount of about 0 to 50 parts by weight as per 100 parts by weight of the flame retardant thermoplastic resin composition according to the present invention.
  • the fluorinated polyolefin resin (E) according to the present invention is prepared by a conventional process, for example; the resin is prepared in an aqueous solvent at 7 ⁇ 71 kg/cm 2 and 0 ⁇ 200 °C, preferably 20 ⁇ 100°C, in the presence of a free radical forming catalyst such as sodium-, potassium-, or ammonium-peroxydisulphate.
  • a free radical forming catalyst such as sodium-, potassium-, or ammonium-peroxydisulphate.
  • the examples of the fluorinated polyolefin resin are polytetrafluoroethylene, polyvinylidenefluoride, tetrafluoroethylene/ vinylidenefluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and ethylene/tetrafluoroethylene copolymer.
  • the fluorinated polyolefin resin may be used in single or in combination as a mixture.
  • the fluorinated polyolefin resin has preferably average particle size of about 0.05 to 1000 ⁇ m and density of about 1.2 to 2.3 g/cm 3 .
  • the fluorinated polyolefin resin functions to form a fibrillar network when the resin composition containing the fluorinated polyolefin resin is extruded, resulting to increase the flow viscosity and to increase the shrinkage during combustion so as to prevent the dripping phenomena.
  • the fluorinated polyolefin resin is used in emulsion state or in powder state.
  • dispersion of the fluorinated polyolefin resin is good, but the process will be somewhat complicated Accordingly, if the fluorinated polyolefin resin could be uniformly dispersed in the entire resin composition to form the fibrillar network structure, it is preferable to use the fluorinated polyolefin resin in powder state.
  • the fluorinated polyolefin resin is used in an amount of about 0.05 to 5.0 parts by weight as per 100 parts by weight of (A)+(B)+(C) of the flame retardant thermoplastic resin composition according to the present invention.
  • additives may be contained in the resin composition of the present invention.
  • the additives include an additional flame retardant, a lubricant, a releasing agent, an anti-dripping agent, an impact modifier, a plasticizer, a heat stabilizer, an oxidation inhibitor, a light stabilizer, a compatibilizer and the like.
  • An inorganic filler such as talc, silica, mica, glass fiber, an organic or inorganic pigment and/or dye can be added too.
  • the additives are employed in an amount of about 0 to 60 parts by weight as per 100 parts by weight of (A)+(B)+(C) of the flame retardant thermoplastic resin composition, preferably about 1 to 40 parts by weight.
  • the flame retardant thermoplastic resin composition according to the present invention can be prepared by a conventional method. All the components and additives are mixed together and extruded through an extruder and are prepared in the form of pellets.
  • the flame retardant thermoplastic resin composition according to the present invention can be applied to electric or electronic goods, automobile parts, office supplies, etc which require good flame retardancy, weld-line strength and impact strength.
  • Bisphenol-A with a weight average molecular weight (M w ) of about 25,000 was used as polycarbonate resin.
  • styrene 71 parts of styrene, 29 parts of acrylonitrile, 120 parts of deionized water and 0.2 parts of azobisisobutylonitrile (AIBN) were blended. To the blend, 0.5 parts of tricalciumphosphate and 0.3 parts of mercaptan-containing chain transfer agent were added. The resultant solution was heated to 80°C for 90 minutes and kept for 180 minutes. The resultant was washed, dehydrated and dried. Styrene-acrylonitrile copolymer (SAN) was obtained.
  • SAN Styrene-acrylonitrile copolymer
  • Comparative Example 1 was conducted in the same manner as in Example 1 except that the phosphorous mixture with different composition was used as in Table 1.
  • Comparative Examples 2-4 were conducted in the same manner as in Example 1 except that a single phosphorous compound was used as in Table 1.
  • Comparative Example 5 was conducted in the same manner as in Example 2 except that a linear phosphazene oligomer was used as in Table 1.
  • Comparative Example 6 was conducted in the same manner as in Example 6 except that a phosphorous acid ester compound only was used as in Table 1.
  • Comparative Example 7 was conducted in the same manner as in Example 6 except that a linear phosphazene oligomer was used as in Table 1.
  • Table 1 Examples Comparative Examples 1 2 3 4 5 6 1 2 3 4 5 6 7 (A) 75 75 75 75 75 95 75 75 75 75 75 95 95 (B) (B 1 ) 12 12 12 12 - 12 12 12 12 12 - - (B 2 ) - - - - - 5 - - - - - - 5 5 (C) 13 13 13 13 13 - 13 13 13 13 - - (D) (d 1 ) 1 3 5 2 2 1 10 13 - - - - - - (d 2a ) 10 8 7 11 - 2 2 - 13 - 8 3 2 (d 2b ) 2 2 1 - 11 1 1 - - 13 2 1 1 (d 3 ) - - - - - - - - - 3 - 1 (E) 0.5 0.5 0.5
  • Example 1-6 and Comparative Examples 1-7 are shown in Table 2.
  • Table 2 Examples Comparative Examples 1 2 3 4 5 6 1 2 3 4 5 6 7 UL94VB(1/16") V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-1 V-2 V-1 V-1 V-1 V-1 Total Flame Out Time (sec) 18 20 21 22 12 13 68 75 124 55 67 66 64 Flexural Strength 835 850 845 840 845 910 820 805 820 825 830 895 900 HDT 85 85 88 90 84 120 91 95 86 80 84 119 120 MFI 39 36 34 34 40 20 30 25 37 42 36 22 21
  • the resin compositions employing a phosphorous mixture of cyclic phosphazene oligomer and phosphorous acid ester show synergistic effect in flame retardancy and flexural strength with no big difference in heat distortion temperature and melt flow index, compared to those employing a single phosphorous compound.
  • the resin composition using a linear phosphazene oligomer shows a poor flame retardancy.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

  1. Flammenhemmende thermoplastische Harzzusammensetzung umfassend:
    (A) etwa 45 bis 90 Gewichtsteile eines Polycarbonatharzes,
    (B) etwa 1 bis 50 Gewichtsteile eines kautschuk-modifizierten Vinylpfropfcopolymers hergestellt durch Pfropfpolymerisation von (b1) etwa 5 bis 95 Gewichtsteile einer Monomermischung bestehend aus etwas 50 bis 95 Gewichts-% wenigstens einer ausgewählt aus der Gruppe bestehend aus Styrol, α-Methylstyrol, halogen- oder alkyl-substituiertes Styrol, C1-8-Methacrylsäurealkylester, C1-8-Acrylsäurealkylester oder einer Mischung daraus und etwa 5 bis 50 Gewichts-% Acrylonitril, Methacrylonitril, C1-8-Methacrylsäurealkyester, C1-8-Acrylsäurealkylester, Maleinsäureanhydrid und C1-4-alkyl- oder phenyl-N-substituiertes Maleimid auf (b2) etwa 5 bis 95 Gewichtsteile eines Kautschukpolymers ausgewählt aus der Gruppe bestehend aus Butadienkautschuk, Acrylkautschuk, Ethylen-Propylen-Kautschuk, Styrol-Butadien-Kautschuk, Acrylonitril-Butadien-Kautschuk, Isopropen-Kautschuk, Copolymer aus Ethylen-Propylen-Dien (EPDM), Polyorganosiloxan-Polyalkyl(meth)acryat-Kautschuk und einer Mischung daraus;
    (C) etwa 5 bis 50 Gewichtsteile eines Vinylcopolymer polymerisiert mit (c1) etwa 50 bis 95 Gewichts-% wenigstens einer ausgewählt aus der Gruppe bestehend aus Styrol, α-Methylstyrol, halogen- oder alkyl-substituiertes Styrol, C1-8-Methacrylsäurealkylester und C1-8-Acrylsäurealkylester und (c2) etwa 5 bis 50 Gewichts-% wenigstens einer ausgewählt aus der Gruppe bestehend aus Acrylonitril, Methacrylonitril, C1-8-Methacrylsäurealkyester, C1-8-Acrylsäurealkylester, Maleinsäureanhydrid und C1-4-alkyl- oder phenyl-N-substituiertes Maleimid;
    (D) etwa 1 bis 30 Gewichtsteile einer Phosphormischung als Flammenhemmstoff, pro 100 Gewichtsteile (A) + (B) + (C), mit (d1) etwa 1 bis 50 Gewichts-% eines cyclischen Phosphazenoligomers enthaltend Verbindungen dargestellt durch die nachfolgende Formel:
    Figure imgb0008
     wobei R1 Alkyl, Aryl, alkyl-substituiertes Acyl, Aralkyl, Alkoxy, Aryloxy, Amino oder Hydroxyl ist, k und m eine ganze Zahl von 1 bis 10 sind, R2 eine Dioxyarylengruppe mit C6-30 oder ein Derivat davon ist und n eine ganze Zahl, die die Anzahl der sich wiederholenden Einheiten angibt, und der durchschnittliche Wert von n in der Mischung der Phosphazenverbindung von 0,3 bis 3 ist; und
    (d2) etwa 99 bis 50 Gewichts-% eines Phosphorsäureesters dargestellt durch die folgende Formel:
    Figure imgb0009
    wobei R3, R4, R6 und R7 eine C6-20-Arylgruppe beziehungsweise eine alkyl-substituierte C6-30-Arylgruppe sind, vorzugsweise eine Phenylgruppe oder eine alkyl-substituierte Phenylgruppe, bei der die Alkylgruppe eine Methyl-, Ethyl-, Isopropyl-, t-Butyl-, Isobutyl-, Isoamyl- oder t-Amylgruppe ist, vorzugsweise eine Methyl-, Ethyl-, Isopropyl- oder t-Butylgruppe, R5 ist eine C6-30-Arylengruppe oder eine alkyl-substituierte C6-30-Arylengruppe, vorzugsweise Resorcinol, Hydroquinon oder Bisphenol-A; und I bedeutet die Anzahl der sich wiederholenden Einheiten und die durchschnittliche Wert von I in der Phosphormischung ist 0 bis 3; und
    (E) etwa 0,05 bis 5,0 Gewichtsteile eines fluorierten Polyolefinharzes mit einer durchschnittlichen Teilchengröße von etwa 0,05 bis 1000 µm und einer Dichte von 1,2 bis 2,3 g/cm3 pro 100 Gewichtsteile (A) + (B) + (C).
  2. Flammenhemmende thermoplastische Harzzusammensetzung, wie in Anspruch 1 definiert, bei der die cyclische Phosphazenoligomerverbindung eine lineare Struktur oder eine Struktur mit einer verzweigten Kette als Hauptkette aufweist.
  3. Flammenhemmende thermoplastische Harzzusammensetzung, wie in Anspruch 1 definiert, bei der R1 Phenoxy und R2 ein Derivat von Catechol, Resorcinol, Hydroquinon oder das Bisphenylendiol, das durch die folgende Formel dargestellt wird, ist:
    Figure imgb0010
     wobei Y eine Alkylengruppe mit C1-5, eine Alkylidengruppe mit C1-5, eine Cycloalkylidengruppe mit C5-6, S oder SO2 ist und z ist 0 oder 1.
  4. Flammenhemmende thermoplastische Harzzusammensetzung, wie in Anspruch 1 definiert, bei der R3, R4, R6 und R7 eine Phenylgruppe oder eine alkyl-substituierte Phenylgruppe sind, bei der die Alkylgruppe ausgewählt wird aus der Gruppe bestehend aus Methyl, Ethyl., Isopropyl und t-Butyl und R5 ist ein Derivat von Resorcinol, Hydroquinon oder Bisphenol-A.
  5. Formteil hergestellt aus der flammenhemmenden thermoplastischen Harzzusammensetzung, wie sie in einem der Ansprüche 1 bis 4 definiert ist.
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